Process aid for melt processable polymers

ABSTRACT

Extrusion processability of non-fluorinated melt-processable polymers is improved by introducing a fluoropolymer process aid by means whereby the weight average particle size of the fluoropolymer is greater than 2 microns as it reaches the extruder die entrance.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of application Ser. No. 09/953,638 filedSep. 17, 2001 and claims the benefit of U.S. Provisional Application No.60/269,247 filed Feb. 16, 2001.

FIELD OF THE INVENTION

The present invention relates to extrusion of non-fluorinatedmelt-processable polymers which contain fluoropolymer processing aids.

BACKGROUND OF THE INVENTION

The melt extrusion of high molecular weight polymers, for example,hydrocarbon polymers and polyamides, into shaped structures such astubing, pipe, wire coating or film is accomplished by well-knownprocedures wherein a rotating screw pushes a viscous polymer meltthrough an extruder barrel into a die in which the polymer is shaped tothe desired form and is then subsequently cooled and solidified into aproduct having the general shape of the die.

In order to achieve low production costs, it is desirable to extrude thepolymer at rapid rates. Higher extrusion rates may be readily obtainedby increasing the rate of revolution of the extruder screw. However,this technique is subject to limitations imposed by the viscoelasticproperties of the polymer substrate. Thus, at very high extrusion ratesan unacceptable amount of thermal decomposition of the polymer canresult. Further, extrudates having a rough surface are often obtainedwhich can lead to formation of an undesirable pattern on the surface ofthe extrudate. These surface defects are also known as melt fracture.Extrusion at elevated temperatures obviates this problem but adds toprocessing costs. Also, cooling of the extrudate becomes problematic. Inaddition, if polyolefins are extruded at temperatures near theirdecomposition points, polymer degradation occurs.

It is desirable, therefore, to find highly efficient means of increasingthe extrusion rate without raising the melt temperature, while producingarticles having smooth surfaces. Changes in extruder and dieconfiguration can improve polymer melt flow, but these modifications arenot always practical or economically feasible. Another approach involvesthe addition of conventional wax-type process aids which reduce bulkviscosity and in some cases improve processing properties. However, theefficiency is marginal and the high levels of additive required oftenadversely affect other properties.

In Blatz, U.S. Pat. No. 3,125,547, it is disclosed that the use of0.01-2.0 wt. % of a fluorocarbon polymer that is in a fluid state at theprocessing temperature (e.g. a fluoroelastomer) will reduce die pressurein extrusions of both high and low density polyethylenes, as well asother polyolefins. Further, use of this additive allows significantincrease in extrusion rates without melt fracture.

Kamiya and Inui, in Japanese Examined Patent Application Kokoku45-30574, cite the use of crystalline fluorocarbon polymers attemperatures below their melting points to eliminate die build-up, butthey disclose nothing regarding other extrusion improvements.

Nishida, et al., in Japanese Patent Application Publication Kokai62-64847, disclose injection molding compositions comprising a mixtureof a) an ethylene/alpha olefin copolymer having a melt flow rate (MFR)of 0.2-200 g/10 minutes and a density of 0.850-0.945 g/cm³, with b)0.001-1% by weight of a fluorinated hydrocarbon polymer having afluorine to carbon ratio of at least 1:2.

Chu, in U.S. Pat. No. 4,740,341, discloses blends having improvedextrudability comprising linear polymers of ethylene having incorporatedtherein small amounts of fluorocarbon polymers and polysiloxanes. Thefluorocarbon polymers have fluorine to carbon ratios of at least 1:2 andare fluid at 120°-300° C.

Larsen, in U.S. Pat. No. 3,334,157, discloses polyethylene which hasbeen modified to improve its optical properties by incorporation of0.015 to greater than 1.7% by wt., based on the mixture, of finelydivided polytetrafluoroethylene.

More recently, improved fluoropolymer process aid compositions have beendisclosed in for example, U.S. Pat. Nos. 4,855,360; 5,587,429 and5,707,569. In these fluoropolymer process aid compositions, a secondadditive, such as a poly(oxyalkylene) or an ionomer resin, is introducedin order to improve extrusion processability of the non-fluorinatedpolymer.

In order to maximize processability improvements, the prior art hasstated that it is desirable that the fluoropolymer process aidcompositions be well dispersed in the non-fluorinated polymer which isto be extruded and that the smaller the particle size of thefluoropolymer, the better the dispersion and thus the better theprocessability. See, for example, “Dynamar™ Polymer Processing AdditiveOptical Microscopy Method for Dispersion Analysis in Polyolefins”(Dyneon 1997), which recommends uniform dispersions and fluoropolymerprocess aid particle sizes 2 microns or less in the extrudate; “Dynamar™Polymer Processing Additives Direct Addition During Resin Manufacture”(Dyneon 12/2000), which recommends uniform dispersions and fluoropolymerprocess aid particle sizes of 3 microns or less in the extrudablecomposition. Similar recommendations have been made in U.S. Pat. Nos.3,125,547; 5,010,130; and 6,048,939.

Due to these references which teach that extrusion processability isimproved by improving the degree of the dispersion of the fluoropolymerprocess aid in the melt processable polymer, and by decreasing theparticle size of the fluoropolymer, much of the prior work in this fieldhas focused on improving the quality of the dispersion and minimizingthe fluoropolymer particle size. Still, there is room for improvement inextrusion processability.

SUMMARY OF THE INVENTION

It has been surprising discovered that extrudable compositions whichcontain predominantly large particle size fluoropolymer actually processbetter, exhibiting fewer melt defects and have faster conditioningtimes, than those compositions which follow the recommendations of theprior art and strive for maximum fluoropolymer dispersion. By“predominantly large particle size fluoropolymer” is meant a weightaverage particle size (as hereinafter defined) of greater than 2microns, but less than 10 microns, as measured at a point immediatelypreceding the die. Extrudable compositions which contain predominantlylarge particle size fluoropolymer can be achieved by a number of means.

Accordingly, one aspect of the present invention is an extrudablecomposition for passing through a die, said composition comprising:

-   -   A) a non-fluorinated melt processable polymer; and    -   B) 25 to 2000 parts per million by weight, based on total weight        of the extrudable composition, of fluoropolymer, said        fluoropolymer having a weight average particle size greater than        2 microns and less than 10 microns, as measured at a point        immediately preceding the die; and wherein said composition is        substantially free of interfacial agent.

Another aspect of the present invention is an extrudable composition forpassing through a die, said composition comprising:

-   -   A) a non-fluorinated melt processable polymer;    -   B) 25 to 2000 parts per million by weight, based on total weight        of the extrudable composition, of a fluoropolymer, said        fluoropolymer having a weight average particle size greater than        2 microns and less than 10 microns, as measured at a point        immediately preceding the die; and    -   C) at least an effective amount of interfacial agent to achieve        a fluoropolymer weight average particle size greater than 2        microns and less than 10 microns, as measured at a point        immediately preceding the die, but no more than a 5:1 weight        ratio of interfacial agent to fluoropolymer.

Another aspect of the instant invention is a process aid masterbatchcomprising:

-   -   A) a non-fluorinated melt processable polymer;    -   B) 1 to 50 weight percent, based on total weight of the        masterbatch, of fluoropolymer; and    -   C) at least an effective amount, to improve processability, of        interfacial agent, but no more than a 5:1 weight ratio of        interfacial agent to fluoropolymer, with the proviso that if the        interfacial agent is a poly(oxyalkylene) polymer, it is present        at less than a 1:1 weight ratio of poly(oxyalkylene) polymer to        fluoropolymer.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to means for improving the extrusionprocessability of non-fluorinated melt processable polymer compositionswhich contain fluoropolymer as a process aid. The term “extrusionprocessability” as used herein refers to the conditioning time (i.e. theelapsed time after extruder start up in which extruded articles exhibita high degree of melt fracture before obtaining an extrudate having asmooth surface, free of melt fracture). Obviously, in order to minimizewaste and reduce costs, a very short conditioning time is desirable.

Examples of non-fluorinated melt processable polymers include, but arenot limited to, hydrocarbon resins, polyamides, chlorinatedpolyethylene, polyvinyl chloride, and polyesters. By the term“non-fluorinated” it is meant that the ratio of fluorine atoms to carbonatoms present in the polymer is less than 1:1. The non-fluorinatedmelt-processable polymers of this invention may be selected from avariety of polymer types. Such polymers include hydrocarbon polymershaving melt indexes (measured according to ASTM D1238 at 190° C., usinga 2160 g weight) of 5.0 g/10 minutes or less, preferably 2.0 g/10minutes or less. The hydrocarbon polymers may be elastomeric copolymersof ethylene, propylene, and optionally a non-conjugated diene monomer,for example 1,4-hexadiene. In general, hydrocarbon polymers also includeany thermoplastic hydrocarbon polymer obtained by the homopolymerizationor copolymerization of a monoolefin of the formula CH₂═CHR, where R is Hor an alkyl radical, usually of not more than eight carbon atoms. Inparticular, this invention is applicable to polyethylene, of both highdensity and low density, for example, polyethylenes having a densitywithin the range 0.85 to 0.97 g/cm³; polypropylene; polybutene-1;poly(3-methylbutene); poly(methylpentene); and copolymers of ethyleneand alpha-olefins such as propylene, butene-1, hexene-1, octene-1,decene-1, and octadecene. Hydrocarbon polymers may also include vinylaromatic polymers such as polystyrene. Because specific hydrocarbonpolymers exhibit differing melt characteristics, the practice of thisinvention may have greater utility in some hydrocarbon polymers than inothers. Thus, hydrocarbon polymers such as polypropylene and branchedpolyethylene that are hot of high molecular weight have favorable meltflow characteristics even at lower temperatures, so that surfaceroughness and other surface defects can be avoided by adjustment ofextrusion conditions. These hydrocarbon polymers may only require theuse of the fluorocarbon polymer extrusion aids and process of thisinvention under unusual and exacting extrusion conditions. However,other polymers such as high molecular weight, high density polyethylene,linear low density polyethylene copolymers, high molecular weightpolypropylene, and propylene copolymers with other olefins, particularlythose with narrow molecular weight distributions, do not permit thisdegree of freedom in variation of extrusion conditions. It isparticularly with these resins that improvements in the surface qualityof the extruded product are obtained with the compositions and processof this invention.

Other non-fluorinated melt-processable polymers that may be a componentof the compositions of this invention include polyamides and polyesters.Specific examples of polyamides useful in the practice of this inventionare nylon 6, nylon 6/6, nylon 6/10, nylon 11 and nylon 12. Suitablepolyesters include poly(ethylene terephthalate) and poly(butyleneterephthalate).

The fluoropolymers useful in the compositions of this invention includeelastomeric fluoropolymers (i.e. fluoroelastomers or amorphousfluoropolymers) and thermoplastic fluoropolymers (i.e. semi-crystallinefluoropolymers). Fluoroelastomers useful in this invention arefluoropolymers that are normally in the fluid state at room temperatureand above, i.e. fluoropolymers which have T_(g) values below roomtemperature and which exhibit little or no crystallinity at roomtemperature. It is preferred, but not essential, to employfluoroelastomers having a fluorine to hydrogen ratio of at least 1:1.5.Fluorinated monomers which may be copolymerized to yield suitablefluoroelastomers include vinylidene fluoride,; hexafluoropropylene,chlorotrifluoroethylene, tetrafluoroethylene and perfluoroalkylperfluorovinyl ethers. Specific examples of the fluoroelastomers whichmay be employed include copolymers of vinylidene fluoride and acomonomer selected from hexafluoropropylene, chlorotrifluoroethylene,1-hydropentafluoropropylene, and 2-hydropentafluoropropylene; copolymersof vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene or1- or 2-hydropentafluoropropylene; and copolymers oftetrafluoroethylene, propylene and, optionally, vinylidene fluoride, allof which are known in the art. In some cases these copolymers may alsoinclude bromine-containing comonomers as taught in Apotheker and Krusic,U.S. Pat. No. 4,035,565, or terminal iodo-groups, as taught in U.S. Pat.No. 4,243,770. The latter patent also discloses the use of iodogroup-containing fluoroolefin comonomers. When fluorinated monomers arepresent in these copolymers in certain molar ratios, the glasstransition temperature of the polymer is near or below 0° C., and thecompositions are useful elastomers that are readily available articlesof commerce.

Semi-crystalline fluoropolymers which may be used in the inventioninclude, but are not limited to poly(vinylidene fluoride), homopolymersand copolymers of tetrafluoroethylene (such as Teflon® FEP fluorocarbonresin, and copolymers of tetrafluoroethylene, propylene and, optionally,vinylidene fluoride).

Multimodal fluoropolymers, such as those disclosed in InternationalPatent Publication WO 00/69967, may also be employed as thefluoropolymer in the compositions of this invention. By “multimodal” ismeant that the fluoropolymer has at least two components of discrete anddifferent molecular weights. Both components may be amorphous orsemi-crystalline, or one component may be amorphous and anothercomponent semi-crystalline.

If a single fluoropolymer is used in the compositions of this invention,the fluoropolymer must be substantially molten at the processtemperature of the non-fluorinated host polymer. If a fluoropolymerblend is used, at least one of the blend components must meet thiscriterion. To function effectively as a process aid at weight averageparticle sizes as low as about 2 microns, an upper limit on theviscosity of the molten component of the process aid exists. If themolten component of the process aid is a fluoroelastomer, the Mooneyviscosity (measured per ASTM-D1646 at 121° C., large rotor, condition ML1+10 minutes) must be 80 or less, preferably 60 to 80. If the moltencomponent of the process aid is semi-crystalline, the melt index (ASTMD-1238, 265° C., 5 kg weight) must be greater than 0.5 dg/min,preferably in the range 0.5 to 3 dg/min. Fluoropolymers becomeincreasingly difficult to spread on the internal surfaces of processequipment as the fluoropolymer viscosity increases. Thus, beyond theseviscosity limits, the process aid performance is degraded unless theweight average particle size of the fluoropolymer delivered to the dieis extremely large, greater than about 10 microns. Fluoropolymerparticles of this size are often large enough to form surfacedistortions or internal flaws in the extrudate. Therefore, it isdesirable to restrict the weight average particle size of thefluoropolymer to less than 10 microns.

In the present invention it is desirable to control the weight averageparticle size of fluoropolymer process aid in the composition which isto be extruded so that it is greater than 2 microns, but less than 10microns, when the composition reaches a point in the process immediatelypreceding the die (i.e. at the die entrance). Preferably, the weightaverage particle size of fluoropolymer is greater than 4 microns (andmost preferably, greater than 6 microns) as measured just prior to thedie.

Weight average particle size (diameter) is defined by the equationA=(Σw _(i) X _(i)),wherein A is weight average particle size (diameter); w_(i) is theweight fraction of fluoropolymer particles in a particular sample havingparticle diameters in the range defined by X_(i); and X_(i) is specifiedby dividing the particle diameter range in the sample into i intervalsand assigning X_(i) to be the mean particle diameter of the range ofparticle sizes encompassed by the i^(th) interval. W_(i) may bedetermined by a number of means including a) examining fluoropolymerdispersions using a light microscope, a digitizing camera, and a hotstage to melt the carrier resin, b) using a Confocal Laser microscope toimage the fluoroelastomer particles in three dimensions, followed bysize analysis using appropriate software c) analyzing photomicrographsof fluoropolymer dispersions, or d) by first dissolving the matrixresin, separating the fluoropolymer particles from matrix polymer resin,and then measuring particle size distribution by light scattering orsome other known technique. When w_(i) is calculated fromphotomicrographs, absent other knowledge to the contrary, the particlesmay be assumed to be substantially spherical in shape.

Although statistical moments of distributions are widely used in polymerscience, these tools have not heretofore been applied to the field offluoropolymer process aids. For example, in The Elements of PolymerScience and Engineering by Alfred Rudin (Academic Press, 1982) thenumber average molecular weight of a polymer is defined by the ratio ofthe first moment to the zeroth moment of the molecular weightdistribution, while the weight average molecular weight is defined bythe ratio of the second moment to the first moment of the molecularweight distribution. The number and weight averages correspond to thearithmetic mean of the number or weight distribution. Characterizing thefluoropolymer particle size distribution using a weight average ratherthan a number average is appropriate for the present invention, because,as described by Migler et al. (J. Rheol. 45(2), March/April 2001),fluoropolymer process aids function by depositing a fluoropolymercoating on internal die surfaces. Since the present invention is basedon the discovery that, at equal fluoropolymer concentrations, largeparticles transfer fluoropolymer mass to the die surface more quicklythan small particles, the salient quality of a particle distribution forprocess aids is a measure of where the majority of the fluoropolymermass lies in the size distribution.

Furthermore, because statistical methods for particle size analysis havenot been previously used in the field, prior references generallydescribe the fluoropolymer dispersion in terms of a size range.Unfortunately, a size range provides no information as to the weightaverage particle size of the distribution, other than indicating thatthe weight average must lie within the given range. A prior artextrudable composition that contains a minor amount of fluoropolymerparticles greater than 2 microns in size, but having a majority offluoropolymer particles less than 2 microns, would not provide theimprovement in conditioning time seen with compositions of the presentinvention.

For ease of processing, fluoropolymer process aids are often in the formof a masterbatch, rather than neat, when they are added to thenon-fluorinated melt processable polymer to form the composition whichis to be extruded. A master batch is a dispersion (mixture) offluoropolymer in a diluent polymer. The diluent polymer can be the samenon-fluorinated melt-processable polymer that is to be extruded, or itcan be a second non-fluorinated melt processable polymer that does notdeleteriously affect the extrusion behavior of the first non-fluorinatedmelt processable polymer/process aid composition. Masterbatchestypically contain 1-50 wt. % (preferably 1-30 wt. %) fluoropolymerprocessing aid (based on the total weight of the masterbatch).Masterbatches can be made, for example, by mixing the appropriate amountof fluoropolymer with diluent polymer in a mixer, such as a Banbury®mixer, at a temperature above the melting point of the non-fluorinatedmelt processable polymer, so as to form a masterbatch. Depending onmasterbatch concentration, composition, and mixing conditions, theweight average particle size of fluoropolymer in a masterbatch of theprior art may be less than or greater than 2 microns. In preparingmasterbatches that may be employed in the extrudable compositions ofthis invention, it is important to minimize exposure of thefluoropolymer to high shear, particularly for low fluoropolymerconcentration masterbatches (i.e. those containing less than about 5 wt.% fluoropolymer). Otherwise, the weight average particle size of thefluoropolymer may be reduced to less than 2 microns in the masterbatch.

The rate at which a fluoropolymer process aid masterbatch is fed to anextruder is controlled so that the level of fluoropolymer in theresulting extrudable composition is between 25 to 2000 ppm (preferably25 to 1000 ppm) by weight, based on the total weight of the extrudablecomposition.

There are several possible means for achieving the desirablefluoropolymer weight average particle size of greater than 2 microns,but less than 10 microns, as measured in the extrudable composition at apoint near the die. One such means, an aspect of this invention, is anovel extrudable composition comprising a non-fluorinated meltprocessable polymer; and 25-2000 ppm by weight, based on the totalweight of the extrudable composition, of fluoropolymer, wherein thefluoropolymer has a weight average particle size greater than 2 microns(preferably greater than 4 microns, most preferably greater than 6microns), but less than 10 microns, as measured at a point immediatelypreceding the die (i.e. the die entrance). This extrudable compositionis substantially free of interfacial agent (as hereinafter defined). By“substantially free” is meant 0 to about 10 parts per million by weightinterfacial agent, based on the total weight of the extrudablecomposition.

This extrudable composition of the invention may be made in a processwherein fluoropolymer (having a weight average particle size prior tointroduction into the extruder of greater than 2 microns, preferablygreater than 4 microns, most preferably greater than 6 microns) isintroduced (either neat or in a masterbatch) to and mixed withnon-fluorinated melt processable polymer to form an extrudablecomposition containing 25-2000 ppm fluoropolymer. Mixing thenon-fluorinated polymer with the fluoropolymer, and pumping theresulting composition to the die, is performed in such a manner that thefluoropolymer is exposed to high shear for a minimal amount of time andthus, the fluoropolymer weight average particle size remains greaterthan 2 microns when the extrudable composition reaches the die entrance.

Care must be taken not to over process the extrudable compositioncontaining the fluoropolymer before it reaches the die entrance.Otherwise, what may have started out as a large weight average particlesize fluoropolymer when it was fed to the extruder, could be on theorder of 1 micron (or less) when it reaches the die. Over processingincludes any process wherein the fluoropolymer process aid is exposed todispersive mixing conditions for too long. Over processing can takeplace in some types of polymer mixing devices such as fully intermeshingtwin screw extruders, Buss Kneaders®, single screw extruders equippedwith screws which incorporate built in mixing devices (e.g. Maddockelements, pin mixers, ring elements, reverse flights), and single screwextruders having fine screen packs or restrictive dies that generatehigh pressure (i.e. >20 MPa) at the extruder exit. Preferably,processing will take place in a single screw extruder, with or withoutscrew mounted mixing elements. Most preferably, screw mounted mixingelements and downstream mixing devices should be absent.

Because all extrusion processes may potentially degrade thefluoropolymer particle size, it is desirable to introduce thefluoropolymer to the extruder while in a particularly coarse state, suchas a pellet, coarsely ground powder, or a masterbatch containingfluoropolymer particles having a weight average particle size muchgreater than 2 microns. To minimize dispersion and improve conditioningspeed, the fluoropolymer viscosity at the extrusion processingconditions should be about equal to or greater than the viscosity of thenon-fluorinated melt processable thermoplastic polymer. For example, acoarsely ground fluoropolymer may be dry blended at 25 ppm to 2000 ppmwith a polyethylene resin, and fed to a single screw extruder. Theextruder screw should have a low compression ratio (3:1 or less) andcontain no mixing elements. Downstream of the screw, the polymer flowpath should present minimal restrictions other than the die itself.

A preferred means in which to ensure that the weight average particlesize of the fluoropolymer will be greater than 2 microns when it reachesthe die is to introduce an interfacial agent into either the masterbatchor the extrudable composition. The interfacial agent somehow stabilizesthe particle size of the fluoropolymer so that the fluoropolymerparticles are less sensitive to high shear environments such as mixing.By “interfacial agent” is meant a thermoplastic polymer which ischaracterized by 1) being in the liquid state (or molten) at theextrusion temperature, 2) having a lower melt viscosity than both thenon-fluorinated melt processable polymer and fluoropolymer process aid,and 3) freely wets the surface of the fluoropolymer particles in theextrudable composition. Examples of such interfacial agents include, butare not limited to i) silicone-polyether copolymers; ii) aliphaticpolyesters such as poly(butylene adipate), poly(lactic acid) andpolycaprolactone polyesters (preferably, the polyester is not a blockcopolymer of a dicarboxylic acid with a poly(oxyalkylene) polymer); iii)aromatic polyesters such as phthalic acid diisobutyl ester; iv)polyether polyols (preferably, not a polyalkylene oxide) such aspoly(tetramethylene ether glycol); v) amine oxides such as octyidimethylamine oxide; vi) carboxylic acids such as hydroxy-butanedioic acid; vii)fatty acid esters such as sorbitan monolaurate and triglycerides; andvii) poly(oxyalkylene) polymers. As used herein, the term“poly(oxyalkylene) polymers” refers to those polymers and theirderivatives that are defined in U.S. Pat. No. 4,855,360. Such polymersinclude polyethylene glycols and their derivatives.

A preferred aliphatic polyester interfacial agent is a polycaprolactonehaving a number average molecular weight in the range 1000 to 32000,preferably 2000 to 10000, and most preferably 2000 to 4000.

The interfacial agent is a relatively low molecular weight ingredientwhich, for a particular system of fluoropolymer process aid andnon-fluorinated melt processable polymer, preferentially locates at theinterface between these two polymers. While not wishing to be bound byany particular explanation, it is believed that the interfacial agentfunctions by reducing the shear stress on the fluoropolymer particlesduring melt processing of the non-fluorinated polymer, thereby reducingthe ability of melt processing equipment to affect the dispersion of thefluoropolymer. The interfacial agent may be introduced to the mixture offluoropolymer and non-fluorinated polymer at any point up to andincluding the final melt shaping process, with the proviso that at thepoint of introduction, the weight average particle size of fluoropolymerparticles must be greater than 2 microns. It is most desirable tocombine the fluoropolymer and interfacial agent in a masterbatching stepwhere both ingredients are present at high concentration (i.e. atgreater than or equal to 1 wt. %, based on the total weight ofmasterbatch), so that the wetting of the fluoropolymer surface in themixture occurs quickly.

Accordingly, another aspect of the invention is a masterbatch comprisinga) non-fluorinated melt processable polymer; b) 1 to 50 weight percent,based on the total weight of the masterbatch, of fluoropolymer; and c)at least an effective amount of an interfacial agent to improveprocessability. By “at least an effective amount” is defined as anyamount of interfacial agent present in the masterbatch which, when themasterbatch is mixed with a non-fluorinated melt processable polymer,results in an extrudable composition that provides a measurablereduction in conditioning time for removal of all surface melt fractureduring extrusion, as compared to the same composition not containinginterfacial agent. Generally, there is no benefit in extrusionprocessability by incorporating into the masterbatch more interfacialagent than 5 times the level of that of the fluoropolymer process aid(i.e. a weight ratio of interfacial agent to fluoropolymer up to 5:1 inthe composition). If the interfacial agent is a poly(oxyalkylene)polymer, preferably the weight ratio of interfacial agent tofluoropolymer is less than 1:1 in the masterbatch.

Another aspect of the present invention is a composition comprising a)fluoropolymer and b) polycaprolactone. Such a blend may be utilized inthe manufacture of masterbatches, or as an additive to be introduceddirectly into an extrudable composition. Preferably, the weight ratio ofpolycaprolactone to fluoropolymer is no greater than 5:1 in thiscomposition. Preferably, the polycaprolactone employed in this aspect ofthe invention has a number average molecular weight in the range 1000 to32000, more preferably 2000 to 10000, and most preferably 2000 to 4000.These blends may be made by a variety of methods including admixingpellets or powders of fluoropolymer and polycaprolactone, orencapsulating fluoropolymer granules with a coating of polycaprolactone.

Another aspect of the present invention is an extrudable composition forpassing through a die, said composition comprising a) non-fluorinatedmelt processable polymer; b) 25 to 2000 ppm by weight, based on thetotal weight of the extrudable composition, of fluoropolymer, saidfluoropolymer having a weight average particle size (as measured at apoint immediately preceding the die) of greater than 2 microns(preferably greater than 4 microns, most preferably greater than 6microns), but less than 10 microns; and c) at least an effective amountof an interfacial agent to achieve a weight average fluoropolymerparticle size greater than 2 microns, but less than 10 microns, asmeasured at a point immediately preceding the die. The upper level ofinterfacial agent present in the extrudable composition is a weightratio of interfacial agent to fluoropolymer of 5:1, and, preferably, thelatter ratio is less than 1:1 when the interfacial agent is apoly(oxyalkylene) polymer.

The compositions of the invention are particularly useful in extrusionsof melt processable polyolefins. Such extrusion processes are commonlyused in manufacture of blown films and wire and cable jacketing.

EXAMPLES

The following examples illustrate the significant improvement inextrusion processability, as evidenced by lower conditioning times andlower die pressure, when the weight average particle size offluoropolymer process aid is greater than 2 microns as it reaches thedie.

The materials used in these examples were as follows:

The non-fluorinated melt processable polymer was either (a) a highmolecular weight linear low density polyethylene, i.e. a linear lowdensity (d=0.918) copolymer of ethylene and 1-butene having a melt index(ASTM D-1238, condition E) of 1.0 (hereinafter referred to as“LLDPE-1”), or (b) an ethylene-octene linear low density polymer with amelt index of 25.0, and density 0.917 g/cc (LLDPE-2).

The fluoropolymer process aids used were fluoroelastomers, either aloneor in combination with a thermoplastic fluoropolymer. Fluoroelastomers(FE-1, FE-2, and FE-3) were copolymers of vinylidene fluoride andhexafluoropropylene, in a 60/40 weight ratio. FE-1 had a Mooneyviscosity of 55, FE-2 had a Mooney viscosity of 40, and FE-3 had aMooney viscosity of 75 (all measured per ASTM D-1646, large rotor,condition ML 1+10 minutes, measured at 121° C.). The thermoplasticfluoropolymer (FP) was a low molecular weight, non-fibrillating grade ofpolytetrafluoroethylene, with a peak melting temperature (ASTM D4894) of325° C.±5° C.

Some of the interfacial agents employed were polycaprolactone (PCL)polymers that were derived from the ring opening reaction ofepsilon-caprolactone, initiated by 1,4-butanediol.

-   PCL-1 was a 1000 number average molecular weight polycaprolactone    diol.-   PCL-2 was a 2000 number average molecular weight polycaprolactone    diol.-   PCL-3 was a 4000 number average molecular weight polycaprolactone    diol.-   PCL-4 was a 32000 number average molecular weight polycaprolactone    diol.

Another interfacial agent used in the examples was PEG, a polyethyleneglycol with a number average molecular weight of about 8000, sold underthe trade name Carbowax™ 8000 (Union Carbide Corp.)

Example 1

Masterbatches of the invention (coded MB-1, etc.) and controls (codedMB-A, etc.) were produced from the compositions shown in Table I (valuesare weight percent), using a 28 mm co-rotating twin screw extruderoperating at 300 revolutions per minute (rpm) and 200° C. to melt mixthe ingredients. The extruded strands were cooled in a water bath andpelletized.

TABLE I Material MB-A MB-1 MB-2 MB-3 MB-4 MB-B MB-C MB-D MB-5 MB-6 MB-ELLDPE-1 99 98.75 98.5 98 96 96.39 98.5 95 95 95 95 FE-1 0.96 0.96 0.960.96 0.96 0 0 0 0 0 0 FE-2 0 0 0 0 0 0 1.5 1.5 1.5 1.5 1.5 FP 0.04 0.040.04 0.04 0.04 0 0 0 0 0 0 PCL-1 0 0 0 0 0 0 0 3.5 0 0 0 PCL-2 0 0 0 0 00 0 0 3.5 0 0 PCL-3 0 0.25 0.5 1 3 3.61 0 0 0 3.5 0 PCL-4 0 0 0 0 0 0 00 0 0 3.5

Extrusion processability evaluations were carried out on a C. W.Brabender Instruments Inc. Computerized Plasti-Corder equipped with a19.1 mm (¾ inch) diameter extruder with a 25/1 length to diameter ratio.Unless otherwise specified, the extruder screw had 15 feed flights, 5transition flights, 5 metering flights, a compression ratio of 3:1, andno mixing elements. Operating parameters were controlled by fourindependent heating zones, one pressure transducer, and atorque-measuring drive unit equipped with 1-120 rpm capability. Theextruder was fitted with a 2.54 cm (1 inch) slot die having a 0.51 mm(0.020 inch) die gap and a land length of 1.016 cm (0.4 inches), toproduce a continuous polyethylene tape. This equipment set-up containedno elements specially intended to promote mixing during extrusion. Thusthe equipment provided a high sensitivity to the particle size of thefluoropolymer process aid fed to the extruder, since the extruder hadonly limited ability to alter the size of the fluoropolymer before itreached the die.

In operation, the die temperature was set to 204° C., and the extruderbarrel temperatures were set at 160° C. (feed zone), 180° C. (middle),and 200° C. (exit). The extruder screw speed was held constant at 45rpm. Die pressure and extruder torque were recorded by computerautomatically at one minute intervals throughout the test. Experimentswere carried out by establishing a baseline condition of 100% meltfracture using pure LLDPE-1 feed (i.e. contained no fluoropolymerprocess aid or interfacial agent), and allowing the extruder output anddie pressure to reach steady state. The feed was then switched to a dryblend of the LLDPE-1 and masterbatch under evaluation, and a digitaltimer with a one second readout was started to measure the conditioningtime. Samples of extrudate were taken at intervals, and the percent ofsurface area of the tape covered by melt fracture defects was evaluatedby visual inspection with a 30× illuminated magnifying lens. The testswere run for 60 minutes. Extrudate samples were always taken at the 60minute mark, and the time required to achieve 0% melt fracture (i.e. theconditioning time) was recorded if this state was achieved during thetest.

Upon completion of the test, the feed was switched to an abrasive purgecompound containing 60% synthetic silica in polyethylene (KCG60, A.Schulman Inc.) to remove fluoropolymer process aid from the extruder anddie. After a thorough purging (30 to 45 minutes), the pure LLDPE-1 wasre-introduced to establish that the baseline conditions of die pressure,output, and melt fracture had been recovered. To ensure that no silicaparticles remain in the test extruder to potentially obscure theparticle size measurements, the extruder and die were then disassembledand cleaned. The extruder barrel was scrubbed with a wire brush,followed by a cloth damp with xylene. All polymer was removed from thescrew and die using high pressure air containing a particulate blastingmedia.

Fluoroelastomer particle size distributions were measured using a NikonMicrophot-SE compound microscope operated with standard reflective lightand a 40× objective configured for digital acquisition. Overallmagnification was 400×. Illumination was provided by a Nikon Transformermodel UN set to position 4. Images were captured and digitized using aSony video camera model DXC-760 MD with DXC-750 control, and displayedon a computer monitor using a Matrox Meteor Graphics card withIntellicam 2.0 software. A portable hot stage, model HS400 from InstecInc., was placed on the microscope stage. The hot stage temperature was220° C.

To measure a particle size distribution, a thin slice (˜0.5 mm) of thesample to be analyzed was cut with a razor blade, perpendicular to thedirection of extrusion. The slice was placed on the hot stage platen andallowed to equilibrate. Fluoroelastomer particles were imaged by movingthe focal plane through the thickness of the sample. To avoid countingdirt particles, only focal planes within the interior of the sample wereanalyzed. When analyzing extrudable compositions, typically five tofifteen fluoroelastomer particles were in focus at any given focalplane. In some samples, the fluoroelastomer particles were not uniformlydistributed within the sample, and a survey was taken at lowermagnification to determine areas rich in fluoroelastomer particles.Masterbatch compositions contained greater numbers of particles at agiven focal plane, depending on the masterbatch concentration.

Fluoroelastomer particle sizes were determined by visually estimatingthe diameter relative to a 10 micron scale with 2 micron incrementsdisplayed along side the sample image on the computer screen. Thesmallest particle size categorized by this technique was 0.5 microns.Particle diameters greater than 0.5 microns were measured to the nearestwhole micron. Up to particle sizes of about 5 microns, the particlesappeared uniformly circular on the digitized image. Although manyparticles larger than 5 microns were circular, some large particles hadan elongated shape. In these cases, the longest dimension was taken tobe the particle diameter. From time to time, an angular or irregularparticle was found in a sample. These were not analyzed, under theassumption that they were not fluoroelastomer. For each sample, 100 to150 particles were counted.

Control samples of extrudate with no fluoroelastomer were taken at thestart of each extrusion run. These were examined as described above toensure there was no contamination that could affect the particle sizemeasurements. At the completion of the extrusion test (i.e., after meltfracture had completely cleared, or 60 minutes of extrusion hadelapsed), the extruder screw speed was set to zero and the die wasremoved. The screw speed was then set to about 10 rpm, so that thematerial in the die adapter (Oust upstream of the die) was slowlyextruded. About five grams of extrudate were collected in this manner,allowed to cool without disturbance, and subsequently used tocharacterize the fluoroelastomer particles being delivered to the diefor that extrusion test.

Masterbatches MB-1, MB-2, MB-3, and MB4 of the invention were formedinto extrudable compositions of the invention (EC-1-EC4) by dry blendingthem, at 2 wt. % level, with LLDPE-1, thus yielding compositionscontaining 200 ppm total of fluoropolymer process aids FE-1 and FP andbetween 50 to 600 ppm interfacial agent PCL-3. A control extrudablecomposition (EC-A) was made in the same manner by blending 2 wt. %masterbatch MB-A with LLDPE-1, resulting in a composition containing 200ppm fluoropolymer process aid, but no interfacial agent. A secondcontrol extrudable composition (EC-B) was made by dry blendingmasterbatch MB-B, at 1.33 wt. % level, with LLDPE-1, yielding acomposition which contained 480 ppm interfacial agent PCL-3, but nofluoropolymer process aid. Table II lists the results of extrusiontesting and particle size measurements, as described above, on theseextrudable compositions.

TABLE II % Melt Weight Average Particle size range fracture at DiePressure Extrudable particle size delivered delivered to the die testConditioning (MPa) at test Composition Masterbatch to the die (microns)(microns) completion Time (min) completion EC-A MB-A 1.8 0.5 to 3 3 >6013.2 EC-1 MB-1 2.9 0.5 to 4 0 41 11.5 EC-2 MB-2 3.7 1 to 6 0 44 10.9EC-3 MB-3 2.7 1 to 4 0 30 10.7 EC-4 MB-4 4.9 1 to 8 0 11 11.2 EC-B MB-Bno particles no particles 100 >60 19.9

The results in Table II show that the extrudable compositions of theinvention (EC-1-EC4), containing both interfacial agent PCL-3 andfluoropolymer process aids FE-1 and FP, decreased the time required toeliminate melt fracture defects on the extruded tape and decreased diepressure versus Control EC-A which contained only fluoropolymer processaid without interfacial agent. Control EC-B, having only interfacialagent PCL-3 and no fluoropolymer process aid, had no effect on meltfracture defects, and die pressure was worse (i.e. higher) than that ofControl EC-A. PCL-3 effectively prevented the reduction of thefluoroelastomer particles during masterbatch compounding and theextrusion experiment to a weight average size below 2 microns, therebyimproving the performance of the fluoroelastomer process aid. Inaddition, the performance of the process aids correlated with the weightaverage fluoroelastomer particle size delivered to the die during theextrusion experiment. For example, although EC-A did contain particleslarger than 2 microns, there were insufficient quantities of theseparticles to raise the weight average particle size above the 2 micronthreshold, and this extrudable composition showed inferior conditioningtime, as well as higher die pressure at test completion as compared tothe compositions of the invention containing fluoroelastomer particleswith a weight average size of greater than 2 microns.

Example 2

Extrudable compositions of the invention (EC-5 and EC-6) and controlextrudable compositions (EC-C - EC-E) were made from masterbatches MB-5,MB-6, MB-7, MB8 and MB-C (respectively) by dry blending 1.33 wt. %masterbatch with LLDPE-1, resulting in 200 ppm FE-2 fluoropolymerprocess aid and either 0 (in Control C) or 465 ppm PCL interfacial agent(in EC-5 and EC-6, and in EC-D and EC-E) of varying molecular weight inall the extrudable compositions. Table III lists the results ofextrusion testing and particle size measurements performed according tothe methods described in Example 1.

TABLE III % Melt Weight Average fracture at Die Pressure Extrudableparticle size delivered test Conditioning (MPa) at test CompositionMasterbatch to the die (microns) completion Time (min) completion EC-CMB-C 1.6 50 >60 18.7 EC-D MB-D 1.5 1 >60 13.4 EC-5 MB-5 6.5 0 9 10 EC-6MB-6 5.1 0 9 11.2 EC-E MB-E 1.9 30 >60 16.4

The results listed in Table III show that the entire molecular weightrange tested of the PCL interfacial agent (in combination withfluoropolymer process aid) improved the extrusion processability byreducing melt fracture, conditioning time and die pressure. However, atleast when used in combination with fluoropolymer FE-2, polycaprolactonehaving number average molecular weights of 2000 (PCL-2) and 4000 (PCL-3)were more effective than polycaprolactone having number averagemolecular weights of either 1000 or 32,000 in preventing the breakdownof fluoroelastomer particles to small sizes. The increasedfluoroelastomer particle size (greater than 2.0 microns weight average)in turn provides faster elimination of melt defects and lower diepressures in formulations containing PCL-2 or PCL-3, as compared withthose containing PCL-1 or PCL4.

Example 3

Masterbatch compositions shown in Table IV (values are in weightpercent) were produced using a 28 mm co-rotating twin screw extruderoperating at 300 rpm and 200° C. to melt mix the ingredients. Theextruded strands were cooled in a water bath and pelletized. Byincreasing the concentration of FE-1 in the masterbatch, the size of thefluoroelastomer particles in the masterbatch was increased. When theamount of dispersive mixing in the Brabender®) extruder was insufficientto reduce the large fluoroelastomer particles present in the masterbatchto a weight average diameter of less than 2 microns (at the dieentrance), masterbatches containing large particles eliminated meltfracture defects more quickly than masterbatches containing smallfluoroelastomer particles. MB-9 and MB-10 demonstrated that thefluoroelastomer particle size in the masterbatch may also be increasedby maintaining low fluoroelastomer concentration (same as MB-G andMB-H), while increasing the melt index of the polyethylene used duringcompounding of the masterbatch. A third method of producing largefluoroelastomer particles and delivering them to the die wasdemonstrated by MB-11, in which a higher viscosity fluoroelastomer(FE-3) was used at relatively low concentration (same as MB-G). Becausethe FE-3 was more difficult to disperse than FE-1, the MB-11 masterbatchdelivered larger fluoroelastomer particles to the die, and eliminatedmelt defects more quickly than MB-G.

TABLE IV MB-F MB-G MB-H MB-7 MB-8 MB-9 MB-10 MB-11 LLDPE-1 99.9 99 95 8875 99 LLDPE-2 99 95 FE-1 0.1 1 5 12 25 1 5 FE-3 1

Extrudable compositions of this invention (EC-7 through EC-11) andcontrol compositions (EC-F, EC-G, EC-H, EC-I and EC-J) were made by dryblending masterbatches MB-7 through MB-11 and MB-F through H withnon-fluorinated melt processable polymer in the proportions shown inTable V (values are in weight percent), to produce ten extrudablecompositions, each having a uniform level of 200 ppm FE-1 or FE-3process aid.

TABLE V EC-F EC-G EC-H EC-7 EC-8 EC-9 EC-10 EC-I EC-J EC-11 LLDPE-1 8098 99.6 99.83 99.92 98 99.6 96.02 99.22 98 LLDPE-2 1.98 0.38 MB-F 20MB-G 2 2 MB-H 0.4 0.4 MB-7 0.17 MB-8 0.08 MB-9 2 MB-10 0.4 MB-11 2

Table VI shows the results of extrusion tests and particle sizemeasurements using compositions EC-F through EC-J, and EC-7 throughEC-11, performed as described previously in Example 1. To confirm theaccuracy of the particle size measurement procedure described in Example1, the fluoroelastomer particles in one of the samples (EC-7) wasadditionally characterized using a Carl Zeiss LSM 510 Confocalmicroscope. Using the 488 nm laser line for excitation, threedimensional images of the particles were captured and analyzed using aKhoros software package. The smallest resolvable particle dimensionusing this equipment was 1 micron.

TABLE VI Weight Average Weight Average particle size in particle size %Melt Die Pressure Extrudable Masterbatch the masterbatch delivered tothe Fracture at test Conditioning (MPa) at test Composition Composition(microns) die (microns) completion Time (min.) completion EC-F MB-F 2 235 >60 17.3 EC-G MB-G 1.7 1.7 40 >60 17.8 EC-H MB-H 2.1 2 30 >60 16.8EC-7 MB-7 4.1 4.8* 0 25 12 EC-8 MB-8 13.1 6.6 0 22 10.6 EC-9 MB-9 4.6 60 20 11.2 EC-10 MB-10 7.3 6.6 0 14 10.5 EC-I MB-G 1.7 nm 20 >60 15.7EC-J MB-H 2.1 nm 5 >60 14.3 EC-11 MB-11 nm 2.3 0 45 12.3 nm = notmeasured *4.56 u measured by confocal laser technique, 1100 particlecounts

The results of extrusion tests on compositions of the invention (EC-7through EC-11) show surprising improvements (vs. controls EC-F throughEC-J) in elimination of melt defects and die pressure reduction.Controls EC-F, G, and H, and Samples EC-7 through 11 show that theseprocess improvements were the result of increasing, above the 2 micronthreshold, the weight average particle size of the fluoroelastomerprocess aid delivered to the die. Measurements of the fluoroelastomerparticle sizes in masterbatches MB-F, G, and H, and MB 7 and 8,confirmed that the fluoroelastomer dispersion became increasingly coarsewith increasing fluoroelastomer concentration in the masterbatch. Withthe extruder configuration used in Examples 1 through 3, increasingweight average particle size of the fluoroelastomer in the masterbatchyielded a corresponding increase in the fluoroelastomer particle sizedelivered to the die.

EC-9 and EC-10 demonstrated that increasing coarseness of thefluoroelastomer dispersion may also be achieved by increasing the meltindex of the polyethylene used for masterbatch production, withoutincreasing the level of fluoropolymer process aid. Use of a high meltindex non-fluorinated melt processable polymer as a carrier for themasterbatch is expected to decrease the dispersive mixing capability ofthe twin screw extruder used for masterbatch production, therebyproducing a coarser fluoroelastomer dispersion than if a lower meltindex (e.g. 1.0 Ml) resin were used. Comparative examples EC-I and Jshowed that equivalent amounts of the 25 melt index LLDPE introducedduring extrusion testing with the finely dispersed masterbatches ofequivalent fluoroelastomer concentration (MB-E and MB-F) did not yieldthe quick elimination of melt defects and large reduction in diepressure shown by compositions of the invention EC-9 and EC-10.

EC-11 demonstrated that by increasing the viscosity of thefluoroelastomer, weight average particle sizes greater than 2 micronsmay be delivered to the die even when the concentration offluoroelastomer in the masterbatch was low. EC-11 also showed that aweight average fluoroelastomer particle size slightly greater than 2microns was more effective than weight average particle sizes of 2microns or less, but not as effective as the very large fluoroelastomerparticles (4 microns and greater) shown in Examples 1 through 3.

Analysis of the fluoroelastomer particle size delivered to the die inEC-7 showed the manual particle counting technique described in Example1 and the automated technique using the Laser Confocal microscope to bein reasonable agreement.

Example 4

The compositions of MB-12 of the invention, and comparativemasterbatches MB-I, and MB-J are shown in Table VII. Values are inweight percent. Masterbatches MB-12 and MB-J were produced on a twinscrew extruder by the process described in Example 1. Masterbatch MB-Iwas produced on a twin screw extruder as described in Example 1, exceptthat the processing temperature was 280° C., rather than 200° C., whileall other compounding parameters remained unchanged. This higherprocessing temperature is typical of the temperature achieved inpelletizing extruders used during commercial polyethylene production.Fluoropolymer process aids are frequently incorporated into polyethyleneresins by direct addition (i.e., no masterbatch is used) into the hopperof the pelletizing extruder.

TABLE VII MB-12 MB-I MB-J LLDPE-1 96 96 96.39 FE-1 1 1 0 PEG 3 3 3.61

The extrudable compositions shown in Table VIII were produced by theprocess described in Example 1. Extrudable composition EC-12 is acomposition of this invention, while the others are comparativecompositions. Values in Table VIII are in weight percent. EC-12, EC-K,and EC-M contained 200 ppm of FE-1 and 600 ppm PEG. EC-L contained 480ppm PEG, but no fluoroelastomer.

TABLE VIII EC-12 EC-K EC-L EC-M LLDPE-1 98 96.34 98.67 98 MB-12 2 MB-G 2MB-I 2 MB-J 1.66 1.33

The extrusion experiment results summarized in Table IX illustrate theeffect of increasing the amount of dispersive mixing during compoundingand extrusion, and the role of an interfacial agent such as PEG inpreventing fluoroelastomer particle break-up in the presence of suchdispersive mixing. In addition, these experiments show that anextrudable composition containing a process aid comprised offluoroelastomer and PEG, where the PEG to fluoroelastomer ratio of theprocess aid is 3.0 and the fluoroelastomer weight average particle sizeis 2 microns or less, does not produce the fast elimination of meltfracture defects and large pressure reduction characterized bycompositions of this invention.

To alter the amount of dispersive mixing during the extrusionexperiments, two different extruder screws were used. The first screw,herein referred to as a metering screw, is described in Example 1. Thesecond screw, herein referred to as a Maddock screw, contained a Maddockmixing element on the discharge end. The Maddock screw was 25:1 L/D with10 feed flights, 5 transition flights, 5 metering flights, and a Maddockmixer encompassing the last five diameters of the screw. To maintainequal extruder output and shear rates in the die, the extruder screwspeed was set to 52 rpm for the Maddock screw, compared with 45 rpm (asdescribed in Example 1) when using the metering screw. All otherextrusion test parameters remained unchanged between runs with differentscrews. Screws containing mixing elements such as a Maddock tip arefrequently used during extrusion of articles such as thin films, toensure good dispersion of additives such as pigments (e.g., TiO2) oranti-block (e.g., silica or talc). Because of the small die gapsnecessary to extrude these thin films, such articles frequently usefluoropolymer process aids to eliminate melt defects and reduce diepressure in order to increase production rates.

TABLE IX Weight Avg. Weight Avg. % Melt particle size in particle sizeFracture at Die Pressure Extruder Extrudable the masterbatch deliveredto the test Conditioning (MPa) at test Screw Composition (microns) die(microns) completion Time (min.) completion type EC-8 13.1 6.6 0 22 10.6Metering EC-8 13.1 1.0 2 >60 12.5 Maddock EC-12 3.0 3.1 0 40 11.2Metering EC-12 3.0 3.5 0 50 11.9 Maddock EC-K 1.7 1.4 30 >60 16.6Metering EC-L no particles no particles 100 >60 19.2 Metering EC-M 2.21.9 25 >60 14.5 Maddock

As indicated in Table IX, EC8, when tested using the Maddock screw,showed that a large fluoroelastomer particle size entering the extruderin the masterbatch is not necessarily sufficient to ensure good processaid performance. In this example, the Maddock screw dispersed thefluoroelastomer to a weight average particle size of 1.0 micron, and thecomposition did not eliminate melt defects within one hour. Note thatEC8, when tested using the metering screw in Example 3, did deliverlarge fluoroelastomer particles to the die, and eliminated melt fracturein 22 minutes. EC-12, in contrast, performed well regardless of thescrew type. MB-12 contained fluoroelastomer particles with a weightaverage particle size of 3.0 microns, and the PEG in EC-12 acted as aninterfacial agent to limit fluoroelastomer particle break-up duringextrusion, so that fluoroelastomer particles with a weight averagediameter greater than 2.0 microns were delivered to the die, independentof screw type. Although EC-12 represents an extrudable composition ofthe invention in Table IX, further increases in the dispersive mixing inthe extruder could reduce the weight average fluoroelastomer particlesize delivered to the die by EC-12 to a value below 2 microns. Both EC-Kand EC-M illustrate this situation. EC-K had the identical LLDPE,fluoroelastomer, and PEG composition as EC-12, but with smallerfluoroelastomer particles (less than 2 micron weight average) deliveredto the die. EC-K was made by blending a masterbatch known to containsmall fluoroelastomer particles with a masterbatch containing PEG. Inthis way, the interfacial agent effect provided by PEG during themasterbatch compounding was eliminated. The results in Table IX showthat when small fluoroelastomer particles are delivered to the die, PEGdoes not improve process aid performance (compare EC-K and EC-G). EC-Kdid not clear melt defects within one hour, nor did it show a largereduction in die pressure, because the weight average fluoroelastomerparticle size delivered to the die was 1.4 microns.

The results in Table IX for EC-M show that the presence of polyethyleneglycol interfacial agent in a masterbatch does not guarantee that anextrudable composition of the invention will be produced from themasterbatch. Although MB-12 and MB-J contained equal levels offluoropolymer and polyethylene glycol, the fluoropolymer particles inMB-J had a smaller weight average size than MB-12 (2.2 microns vs. 3.0microns). The difference in fluoropolymer particle size is believed toresult from the increased compounding temperature used to producemasterbatch MB-J. Because the 2.2 micron weight average particle size ofMB-J was close to the critical 2 micron threshold, even a slight degreeof increased fluoropolymer dispersion in the extruder could cause thefluoropolymer weight average particle size to be reduced below 2.0microns, and thereby impair the performance of the process aid. The datain Table IX for EC-M shows that the Maddock screw reduced the weightaverage fluoropolymer particle size in MB-J from 2.2 microns to 1.9microns as delivered to the die in EC-M, and therefore EC-M is not aseffective as the extrudable compositions of the invention in eliminatingmelt fracture or in decreasing die pressure.

A control extrusion test using only peg (EC-L) confirmed that PEG didnot eliminate melt defects, reduce die pressure, or produce particleswhich could be mistaken for fluoroelastomer.

1. An extrudable composition for passing through a die, said compositioncomprising: A) a non-fluorinated melt processable polymer, wherein saidnon-fluorinated melt processable polymer is a hydrocarbon resin selectedfrom the group consisting of i) polyethylenes, ii) polypropylene, iii)polybutene-1, iv) poly(3-methylbutene), v) poly(methylpentene), and vi)copolymers of ethylene with an alpha-olefin; and B) 25 to 2000 parts permillion by weight, based on total weight of the extrudable composition,of fluoropolymer, said fluoropolymer having a weight average particlesize greater than 2 microns and less than 10 microns, as measured at apoint immediately preceding the die; and wherein said composition issubstantially free of interfacial agent.
 2. The composition of claim 1wherein the fluoropolymer is a fluoroelastomer.
 3. The composition ofclaim 2 wherein the fluoroelastomer has a ML(1+10) at 121° C. up to 80.4. The composition of claim 1 wherein the fluoropolymer is asemi-crystalline fluoropolymer.
 5. The composition of claim 4 whereinthe semi-crystalline fluoropolymer has a melt index (ASTM D1238, 265°C., 5 kg weight) greater than 0.5 dg/min.
 6. The composition of claim 1wherein the weight average particle size of the fluoropolymer is greaterthan 4 microns as measured at a point immediately preceding the die. 7.The composition of claim 6 wherein the weight average particle size ofthe fluoropolymer is greater then 6 microns as measured at a pointimmediately preceding the die.
 8. The composition of claim 1 whereinsaid copolymers of ethylene with an alpha-olefin are selected from thegroup consisting of ethylene copolymers of propylene, butene-1,hexene-1, octene-1, decene-1, and octadecene.